Lubricated thermoplastic resin compositions

ABSTRACT

THIS DISCLOSURE RELATES TO IMPROVED THERMOPLASTIC RESIN COMPOSITIONS WHICH CONTAIN AN ACRYLIC HOMOPOLYMER OR COPOLYMER AS A LUBRICANT.

United States Patcnt'office 3,809,667, Patented May 7, 1974 3,809,667LUBRICATED THERMOPLASTIC RESIN COIVIPOSITIONS Antony W. M. Coaker andElmer E. Cowell, St. Louis, Mo., assignors to Monsanto Company, St.Louis, M0. N Drawing. Continuation-impart of abandoned application Ser.No. 721,203, Apr. 15, 1968. This application Jan. 18, 1971 Ser. No.107,526 a Int. Cl. C08f 45/36, 45/38 US. or. 260-313 R 23 ClaimsABSTRACTOE THE DISCLOSURE This disclosure relates to improvedthermoplastic resin compositions which contain an acrylic homopolymer orcopolymer as a lubricant.

room temperature or slightly above, range from free-fiowing to viscousliquids.

It is well known that polyvinyl aromatic compounds are characterized byimproved properties of toughness when a small amount of a rubberypolymer is added thereto. In order to mold such thermoplastic materials,it is necessary to employ agents which improve moldability, such aslubricants. 1 r p Vinyl chloride polymers are generally hard, rigid,chemically resistant thermopal stic materials and, consequently, arewidely used invarious applications such as chemical processingequipment, pipes, sheeting, moldings, building panels and the like. Amajor disadvantage of this material is its poor impact resistance.Incorporation of relatively large amounts of plasticizers or othercompounding ingredients to improve the physical properties andprocessing characteristics of vinyl chloride resins, has not resulted ina product which is suitable for use where a relatively high impactstrength is required. Additionally, vinyl chloride resins are oftendlffiClJltiO process since the resins tend; to degradebefore reachingthe melt viscosity necessaryto assure good melt flow characteristics. a4

Nylon is a well-known substance and may be readily prepared bypolycondensation of dicarboxylic acids and diamines or bypolycondensation of amino acids to provide high molecular weightpolymers. Particularly desirable nylon is prepared by thepolycondensation of .hexamethylene diamine. and adipic acid or by thepolycondensation of 6-aminocaproic acid. It is also well known thatcommercially prepared nylon is difficult to handle in friction producingoperations. In order to provide nylon possessing high lubricity andlow-friction characteristics, it is necessary to incorporate alubricating agent into the polymericmaterial.- 1

5 Polycarbonate resinshave found many useful applications in theplastics industry because their physical prop erties, coupled withchemical properties, are comparable to those of polystyrene,polymethacrylate and cellulose esters, The polycarbonate resins arewidely employed to fabricate hard, rigid and solid articles such as cambearings, switches, levers, hardware, pipes, fittings, valves, etc. Theindustrial use of these resins is considerably restricted however, sincethe resins are fabricated only with great difficulty. More workable anduseful polycarbonate resin compositions having improved lubricitycharacteristics are provided by addition of a lubricating agent with thepolycarbonate resin. 7

Accordingly, it is a principal object of this invention to provide anadditive for thermoplastic. resin compositions which provides thedesired processing and lubricating properties.

Other objects and advantages of the invention will be apparent to thoseskilled in the art from the following detailed description and claims.

In accordance with this invention, it has been found that the above andstill further objects are accomplished by incorporating a thermoplasticresin and a minor quantity of a liquid homopolymer of an alkyl acrylateor a liquid copolymer of an alkyl acrylate with a dissimilar alkylacrylate component copolymerizable therewith.

The alkyl acrylate esters which are suitable for use in the productionof the processing aids of the present invention are those in which thealkyl group is linear or branch-chained and contains from 1 to about 24carbon atoms. Examples of these esters are methyl acrylate, ethylacrylate,.propyl acrylate, butyl acrylate, tert.-butyl acrylate, pentylacrylate, isopentyl acrylate, hexyl acrylate heptyl acrylate, octylacrylate, Z-ethylhexyl acrylate, decyl acrylate, lauryl acrylate,dodecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, octadecylacrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate and the like.Although any alkyl acrylate monomer falling within the above descriptioncan be employed, it is preferred to employ alkyl acrylates in which thealkyl group contains from about 2 to about 12 carbon atoms andparticularly ethyl acrylate and Z-ethylhexyl acrylate.

Vinyl aromatic resins suitable for use in the presen invention arehomopolymers and copolymers of monovinyl-substituted aromatichydrocarbon compounds having the vinyl group attached to a carbon atomof the aromatic nucleus substituted with one or more groups such asmethyl, ethyl and chloro groups. The preferred polyvinyl aromatic resinsutilize styrene as the vinyl aromatic constituent. In addition, themonovinyl-substituted aromatic constituent may also be admixed orinterpolymerized with from about 1 to about 250 parts by weight, per100, parts by weight of mono-vinyl-substituted aromatic constituent, ofa synthetic rubber such as polybutadiene, polyisoprene, copolymers ofbutadiene and styrene and copolymers of butadiene and a'crylonitrile,which improve the properties of toughness. The preferred polymerssuitable for this invention include styrene, butadiene andacrylonitrile, components such as the copolymer of styrene withbutadiene, and the terpolymenof styrene, acrylonitrile and butadiene.Illustrative examples of substances that can be copolymerized with themonovinyl-substituted aromatic hydrocarbon to form a copolymer are oneor more other ethylenically unsaturated compounds such as ethylene,propylene, isobutylene, butadiene, isoprene, chloroprene, vinyl halidessuch as vinylchloride, vinyl esters such as vinyl acetate and vinylbutyrate, acrylic and amides thereof such-as --methyl acrylate; ethyl"acrylate,-

"polymers of such vinyl compounds with one or more other ethyle'nicallyunsaturated monomers copolymerizable therewith. Illustrative are "thecopolymers of vinyl halide monomers with one or more other monomers suchas ethylene, propylene, isobutylene, b'utadiene and the like; vinylesters of carboxylic acids, e.g.,"vinyl acetate, vinyl pro- "pionate,vinyl butyrate, vinyl benzoate; esters 'of unsaturated acids,"e.g.,alkyl acrylates such as methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate and the corresponding esters of methacrylicacid; vinyl aromatic compounds; e.g., styrene, ortho-chlorostyrene,para-chlorostyrene; dienes such as butadiene and chlorobutadiene;unsaturated amides such as acrylic acid amide and'acrylic acid anilide;unsaturated nitriles such as acrylic acid nitrile; esters ofalpha-beta-unsaturated carboxylic acids, e.g., the methyl, ethyl,propyl, butyl, amyl, hexyl, heptyl, octyl, allyl and phenyl esters ofmaleic, crotonic, itaconic and fumaric acids and the like; vinyl halidessuch as vinylidene bromide, vinylidene chloride and the like. Thosecopolymers in which a predominant portion, i.e., more than 50% by weightof the copolymer, is made from vinyl chloride represent a preferredclass of polymers to be treated according to this invention. Includedwithin the meaning of the phrase vinyl halide polymers are graftcopolymers of vinyl halides on backbones of rubbery ma: terials such aschlorinated polyethylene aswell. as polyblends of vinyl halides withrubbery interpolymers such as a styrene-butadiene interpolymer or'butadiene-acrylonitrile interpolymer. I a

The term polycarbonate resin, as used herein, is meant to designatethermoplastic resins of linear aliphatic, "cycloaliphatic and aromaticpolyesters of carbonic acid, These thermoplastic polycarbonates may beproduced from 'a great number of aliphatic, cycloaliphatic and aromaticdi- -hydroxy compounds. V, Illustrative of the aliphatic'dihydroxycompounds which "caribe employed are ethylene glycol, diethylene glycol,'triethyleneglycol, polyethylene glycol, thioglycol," ethylene dithioglycol, 1,3-propanediol, 1,3-bi1tar1ediol, 1,4- butanediol,1,3-(2-methyl) propanediol, 1,5-pentanediol, 1,6-hexanediol,1,8-octanediol,1,10-decanediol. Illustrative of cycloaliphati'cdihydroxy compounds are 1,4-cycloh'ex& anediol, l,2-cyclohexanedio1,2,2-(4,4-dihydroxydicyclo hexylene )propane and 2,6dihydroxydecahydronaphthaf lone. Illustrative of the aromatic dihydroxycompounds are hydroquinone, resorcinol, pyrocatechol, 4,4edihydroxydiphenyl, l,6 dihydroxynaphthalene, 2,6- dihydroxynaphthalene,-l,4-dihydroxynaphthalene, 1,5 fdihydroxynaphthalene,dihydroxyanthracene, 2,Zf-dihydroxydinaphthyl-l,1' ando,'m,p-hydro'xybenzyl alcohol and the like; dimonohydroxyarynsulfonessuch as di-(4-hydroxyphenyl)sulforie, 'di-(Z-hydroxyphenyl)sulfone,di-(3 -"hydroxyph enyl )sulfone,di-(flhydroxy-il-methylphenyl)sulfone,jdi (4 hy-, droxy-3-methyl'phenyDsultone, di-(2'-hydroxy 4 methy1- phenyl)sulfone,. di 2 hydroxy 1naphthyDs'ulfone di- 4'-hydroxy-3-ethylphenyl) sulfone, di- (4 hydrogiy2 tert.-butylphe nyl) sulfone, di-(4-hydroigy 3terty-lbutylpheriyDsulfone, di 2-hydroxy -"1 naphthylis ulfone and the'like, di-(monohydroxyaryl)alkanes such as;

l,l-di(4-hydroxyphenyl)ethane, 1', 1 -di (4-hydroxyphenyl) propane,1,1-di(4-hydroxyphenyl)butane, '1. :51,1-di(4-hydroxyphenyl)-2-methy1-propane,- 1

2,2-d i(4-hydroxyphenyl)pentane, v

di t4 -hydroxyphenyl) heptane',

di- 4-hydroxyphenyl) -4-methylphenyI-methane, di- 4-hydroxyphenyl-4-ethylphenyl-methane, di-(4-hydroxyphenyl)-4-isopropylphenyl-methane,di-(4-hydroxyphenyl)4-butylphenyl-methane, di- (4-hydroxyphenylbenzylmethane, di- 4-hydroxyphenyl) -a-furylmethane, 2,2-di(4-hydroxyphenyl) octane, 2,2-di(4-hydroxyphenyl)noriane, di-4-hydroxyphenyl -1-u-furyl-ethane, 1,1-di(4-hydroxyphenyl)cyclopentane,2,2-di(4-hydroxyphenyl.)decahyclronaphthalene,

-, 2,2-di(4-hydroXy-3-cyclohexylphenyl 'pr o'pa ne, .2, y v- -is 1 qpy ihi l)hnt n ,a"

1,1-di(4-h ydroxy-3 -methylphenyl)cyclohexafl? 2,2-1di(4-hydroxy-'3-butylphenyl).propa"ne,-, i 2,2-di(4 hydroxy-3aphenylphenyl)proparie,2,2- i(4-hydroxy-2-m mylphenyl)ptqi a e; 1,l-di(4-hydroxy3-methyl-6-butylphenyl)butane, F i '1, ldi(Lhydroxy-Ii-methyl-G-terL-butyIPheriyl)ethane, 1, 1-di(4-hydroxy-3-methyl-6ter-t.-butylphenyl propane, 1, l-di 4-hydroxy -3-methyl;6 tertbutylphenyl) butane, l,1-di(4-hydroxy-3-methyl-6-tertsbutylphenyl)isobutane, 1,1-di(4-hydroxy3-methyl-6-tert. butylphenyl)heptane;l;l-di(4-hydroxy-3-methyl-G-teitz-butylPhenyD l-phenyl-methane, I I. 11, y ye hy1:6rtertchut p y 2 -methyl-2-pentane, I w1,1-di'(4-hydroxy-3-methyl-6-tert.-butylphenyl) 1 J 1 I p-2-ethyl-2-hexan'e," i 1,l-di(4-hydroxy 3-methyl-6-tert.-arnylphenyl)butane,

di-(4 hydroxyphenylfinethane, H 2,2-di(4-hydroayphenyl)propane,'1,l-di(4-hydroxyphenyl)cyclohexane, 1,1 di(4-hydroxy-3methylphenyl)cycloheiiane, I 1,l-di(2-hydroxy-4-methylphenyl)butane, J 12,2-di'(2 hydroxy-4-tert.-butylphenyl)propane, 1 Il,l-di(4-hydroxyphen'yl) 1=phenylethane, i 4

2,2-di(4-hydroxyphenyl)butane;

3,3-di(4 hydroxyphenyl)pentane, 2,]2 di(4-hydroxyphenyl)hekane,"3,3-di(4-hydroxyphenyl)heiiane, 2','Z-'di'(4-hydroxyphenyl)4-rriethylpeiitan 2,2-di(4-hydroxyphenyl)heptane, 4,4-di(4-hydroxyphenyl)heptane, H 2,2-di-(4-hydroxyphenyl)tridecane, A f2,2'-'di(4-hydroxy 3-metliylphenyl)propane, 1 j2,2-di(4-hydroXy-3-methyl 3=isopropylphenyl)butane,2,2-di(3,5-dichloro-4-hydroxyphnyl)prop an' 2,2-di(3,S-dibrorito-4hydro1iyphenyljpropan j di-(3 chloro 4-hydroxyphenyl)methane,1 5 di-'(2-hydroxy 5-fluorophenyl)methane, 5di-(4-hydroxyphenyl-)phenylmet1iane, 1 1, 1-di( 4-hydrox'yphenyl)-1-phenyletliane,

andthelike. I The preferred class of dihydroky conipounds*for use n thepractice of this invention are the arorr'iat'id'dihydrdxy compoundsand-'- in-pa'rt" lar th'e flifrrionohydroxyyr alkanes:

l Polycarbonatesof-the aforesaid 'di '*(mtiriohydroxyaryljalkanes can:be: prepared "by a"'-iii1 mber of metli'od's kho n" to thoseskilledintheart. For eiiarnple'ithedi ems ye" droxyaryl)alkanes can' lber=esterified'witl'i 'carbo 1e *e'd of a base such as lithium, sodium,potassium, and cal- I cium hydroxide or carbonate. The polycarbonatesprecipitate from the aqueous solution.

The di(monohydroxyaryl)alkanes can be reacted with bis-chloro-carbonatesof di(monohydroxyaryl)alkanes in the presence of inertsolvents andacid-binding materials, e.g., tertiary amines.

, Additional examples of thermoplastic materials suitable for use withthis invention include polyvinyl acetate, cellulose ethers such as ethylcellulose, butyl cellulose and benzyl cellulose, cellulose esters oforganic acids having 2 to 4 carbon atoms such as cellulose acetate,cellulose propionate, cellulose butyrate, cellulose acetate-butyrate andcellulose acetate-pripionate and polymers of u-monoolefins'having 2 to24 carbon atoms such as the polymers and copolymers, with at least onedissimilar ethylenically unsaturated monomer, of ethylene, propylene,l-butene, l-octene, l-dodecene, 3-methyl 1 pentene, 3-methyl-4- ethyl lhexene, 3 methyl-l-butene, l-hexene, 5-methyll-hexene, 3,4 dimethyl 7 lpentene, 3,3-dimethyl-lbutene, 1-pentene, 3 methyl 1 hexene, l deceneand the like. Also suitable for use with this invention are polymers ofmethyl; methacrylate, which can be either homopolymers of methylmethacrylate or copolymers of methyl methacrylate with one or more otherethylenically unsaturated monomers copolymerizable therewith, forexample, acrylic acid, methacrylic acid, the 1 to 4 carbon.

resins derived from at least one ethylenically unsaurated monomer,natural resins and 'polycondensation resins.

The processing and lubrication aids utilized in the thermopla'sticcompositions of the 'pr'e's'ent'irivefitioh' include liquidhomopolymersof alkyl acrylate esters-wherein the alkyl radical is linear ofbranch-chained and contains from 1 to about 24 carbon atoms, and liquidcopolymers.

of an alkyl acrylate ester with a dissimilar alkyl acrylate ester. Thecopolymers consist of..(l.) from-about 5 to aboutl to about.-.l2 carbonatoms and (2)--- from about 95 to about 5 percent by weight of adissimilar alkyl acrylate ester wherein the alkyl. constituent containsfrom about 3 to about l8-carbon atoms. In a yet more preferredembodiment of the invention, the useful. lubricating copolymers consistof (1) from about 20 to about 50-percentby weight'of an alkyl acrylateester wherein the. alkyl constituent contains'fromabout 2 to about 8carbon atoms (2) from about to about 50 percent by weight of a disroomtemperature or slightly above. The polymers have an average molecularweight of from about 2,000 to about 10,000, a preferred molecular weightrange being from about 2,000 to about 6,000. A particularly usefulmolecular weight range is from about 3,500 to about 5,000.

Tough or rubbery acrylate materials, such as those frequently used asextenders or impact value modifiers are unsuitable for use aslubricating aids for purposes of this invention.

The modfying homopolymer and copolymer resins described herein, and themethods of their production are well known to the art. The polymers canbe obtained for example, by solution polymerization of a monomer or amixture of two monomers in an inert organic diluent while in contactwith a peroxidic catalyst. Another method for preparing the modifiers isthe mass polymerization process wherein a monomeric ingredient ormixture of monomeric ingredients is mixed with a polymerization catalystat a temperature sufiicient to cause polymerization. Emulsionpolymerization procedures which entail polymerizing a monomer or amixture of monomers as an emulsion in the presence of a suitableemulsifying agent are also suitable for the preparation of the modifiersof this invention. In the emulsion polymerization procedure, which isthe preferred process for preparing the modifying resins, polymerizationof the monomer or mixture of monomers is effected in the presence ofwater which contains dissolved therein a suitable catalyst and anemulsion stabilizing agent. Examples of suitable catalysts includeammonium persulfate, benzoyl peroxide, hydrogen peroxide, sodiumperborate and other water-soluble salts of peroxyacids. The peroxycompounds useful as catalysts may be present in amounts of from about0.02 to 2.0% by weight of the polymerizable compounds. Illustrative ofthe emulsion stabilizing agents useful in this process are variouswetting agents, which are in general organic compounds containing bothhydrophobic and hydrophilic radicals such as sodium alkyl sulfate,sulfated aromatic ether alcohol, sodium alkyl aryl sulfonate, fattyalcohol sulfate, sorbitan trioleate, and the like. The emulsionpolymerization is ordinarily carried out at a temperature in the rangeof from 65 C. to C. depending upon the nature of the polymerizationsystem and the particular catalyst used. The polymeric compositions, ofthe present invention comprise a blend of a major proportion of athermoplastic resin and a minor proportion of a liquid alkyl acrylatehomopolymer or copolymer. More particularly, the compositions comprise ablend of from about 0.001 to 8.0 parts hywei'ght of 'alkyl' acrylatehomopolymer o'r copolymer for-each" parts-by weight of thermoplasticresin. A preferred composition of this invention is one wherein thequantity oflubricating agent ranges from about 0.1 to about 4.0 parts byweight per 100 parts'by weight of thermoplastic resin. Incorporation ofan amount of lubricating agent in excess of 8.0 parts by weight per 100parts by weight of thermoplastic resin employed is 'not useful with thepresent invention since the system thenf becomes overlubricated anddifficult to process.

The polymer blends of the invention arercadily'prepared by mechanicalmethods. The thermoplastic resin and the preformed acrylate homopolymeror copolymer are intimately admixed together on a conventional mixingmachine of'the'type normally used for mixing rubber -or vplasticssuchas. a mill roll, ,an extruder or a Banbury mixer. Preferably, thethermoplastic resin is first placed on the mill roll and'atter a smallrolling bank has formed in the nip of the rolls, the lubricating agentis added.

' The thermoplastic resin and the lubricating agent can also similaralkyl acrylateester wherein the alkyl constituent- I contains from about610 about 12 carbon atoms.

The acrylic lubricants ultilized herein are characterized by theirliquidity, ranging from free-flowing to viscous, at

d be mixed together to form a crude admixture which is then placedo'nthemill roll. Regardless of the method by which the mixing of thesematerials is achieved, it is necessary that the materials 'be mixedtogether or worked under a suificient heat and pressure to insure anefiicient dispersion of the lubricating agent in the thermoplastic resinso as to form a completely homogeneous material. The temperature atwhich this working or mastication is carried out is not critical, aslong as the temperature is at least above the temperature where thethermoplastic resin fuses and below the temperature where decompositionoccurs.

The invention willbe more readily understood by referobtained when thefollowing lubricants are used in place of the lubricants employedtherein: 1

(a) homopolymer of propyl acrylate (b) homopolymer of butyl acrylate l ih t l l te ence to the following examples. There are, of course, many283858 33 5; 8; gg i 223;; other forms of this invention which willbecome obvious (e) homopolymer of decyl acrylate to one skilled in theart, once the invention has been fully (f) homopolymer of tetradecylacrylate disclosed, and it will accordingly be recognized that these (g)homopolymer of hexadecyl acrylate examples are given for the purpose ofillustration only, (h) homopolymer of'docosyl acrylate and are not to beconstrued as limiting the scope of this (i) homopolymer of tetracoxylacrylate invention in any way. d In the following examples, in whichparts are g ven by (J) 255222 55 zif g of p mp Y1 acrylate an 92 iweight unless otherwise stated, the apparent viscosities of (k) 6 op 01y mg I of 85 parts of hexyl acrylate and parts the thermoplasticresinous compositions of the present 15 of propyl arylate i inventionare evaluated according to A.S.T.M. Test No. (l) copolymer of parts ofnonyl acrylate and 80 parts D1703-62 on an Instron Rheometer at atemperature of of docosyl acrylate 190 usmg length ratio 6632 a shear(m) copolymer of parts of heptyl acrylate and 75 parts rate of 67.4sec.- and a die having a mnety degree entry of nonyl acrylate angle.Samples used in determimng apparent viscosities are 20 (n) copolymer of35 parts of amyl acrylate and 65 Parts fiuxed on a two roll mill andground into pellets prior to of dodecyl acrylate measurement on therheometer. Heat distortion tempera- (O) copolymer of 45 parts of decylacrylate and 55 parts tures of the resinous compositions are determinedaccord- 6 56 l d D H T of heptadecyl acrylate mg to 'T 8 D m e 6 action(p) copolymer of 15 parts of dodecyl acrylate and 85 perature ofPlastics Un er Load. 25 parts of butyl acrylate EXAMPLES 1-20 (q)copolymer of 75 parts of dodecyl acrylate and 25 ts of pentadecylacrylate Polyvinyl chloride compositions shown in Tables I and par IIcontaining va ying Proportions of the lubricant of the g gggg gg g gParts of nonyl acrylate and 40 Parts present invention are prepared bymechanically milling the various admixtures, together with desiredprocessing L53 ggg g g :2 arts of ethyl acrylate and 55 Pans aids,stabilizers and the like, on a 6" x 12" Thropp mill Y Y 7 rolls at atemperature of from about 170 to 210 C. A It is found that similareffective apparent viscosity rough mix is first prepared from thepreformed polymers results are also obtained when the polyvinyl chloridein in powdered or pelleted form in a stainless steel beaker. theforegoing examples is replaced in each instance by an The rough mix isplaced on the heated mill rolls and equivalent amount of a copolymer of95 parts of vinyl thoroughly homogenized by intensive hot milling for 5chloride and 5 parts of vinyl acetate, a copolymer of 90 minutes oruntil an adequate dispersion is obtained. The parts of vinyl chlorideand 10 parts of vinylidene chloride compositions are then sheeted andstripped from the mill or a copolymer of 70 parts of vinyl chloride and30 parts rolls. After sufiicient cooling, the sheets are cut into 1 to 2of diethylmaleate. inch squares for convenient feeding to an Abbegrinder for grinding into pellet size. The apparent viscosities andEXAMPLES 2164 heat distortion temperatures of the resulting compositionsFollowing the procedure of Example 1, the resinous are given in Tables Iand II. compositions shown in Tables II-VII are prepared. The Resultssimilar to those obtained with the compositions apparent viscosities andheat distortion temperatures of employed in Examples 1 to 20 of Tables Iand II are the compositions obtained are given below.

TABLE I i 2 3 4 5 c 7 8 9 10 11 Composition, parts by weight:

Polyvinyl chloride 100 100 100 100 100 100 100 100 100 100 10cOrgariotln stabilizer 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 2. 52. 5 M138 1 impact modifier. 10 1O 10 ABS 9 impact modifier 10 10 Lub ii s nt 0.5 2.0 0 3 0 Do: 0.2a 1.5 Do. 1.5 3.0 Apparent viscosity,lJolsesXlO 9. 22 8. 97 1. 83 7. 44 2. 25 9. 53 6. 84 2. 86 4. 75 3.49 1. 33 Heat distortion temperature C.) 67 66 69 68 67 64 66 lMethacrylate-butadiene-styrene terpolymer. iAcrylonitiile-butadiene-styrene terpolyiner.

I copolymer of 50 parts of 2-ethylhexy1 acrylate and 50 parts ofoctadeeyl acrylate (mol. wt.=4,040).

4 Homopclymer of oetadecyl acrylate (mol. wt.=2 470).

6 Homopolyrner of lauryl acrylate (mol. wt.= 1,980

copolymer of 30 parts of ethyl acrylate and parts of 2-ethylliexylacrylate (mol. wt.=4,690).

TABLE II 12 13 14. 15 16 17 18 19 20 Composition, parts by weight:

Polyvin l s-hlnride e 100 100 100 100 100 100 100 100 100 Poly(a-methylstyrenelacrylonitrile) 2 2 2 MB S 1 impact modifier 10 10 10ABS 2 impact modifier 10 10 10 EVCl 3 impact modifier 10 10 10Polyacrylic processing aid 1 1 1 1 1 1 Organotin stabilizer 2 2 2 3 3 3Barium-cadmium stabilizer 2.5 2.5 2.5 Phosphite stabilizer 0. 5 0. 5 0.5 Epoxidized soybean oil 1 1 1 Lubricant; 1 2 1 1 2 Apparent viscosity,poisesxl0" 6. 18 4. 96 8. 47 5. 81 5. 38 4. 12 5. 54 1. 1. 42

l Methacrylate-butadiene-styrene terpolymer. iAcrylonitrile-butadiene-styrene terpolymer. Ethylene-vinyl chloridecopolymer.

4 copolymer of 30 parts of ethyl acr late and 70 arts of Z-eth max 1acry1ate(mo1.wt.=3,500). y p y y TABLE III 21 22 2a 24 25 '26 27 2s 29so 31 a2 Composition, parts by weight Terpolymer of 33 parts ofaerylonitrile, 66 parts of butadiene and 1 part of divinylbenzene 100100 100 100 Copolymer of 74 parts of styrene and 26 parts ofacrylonitrile 100 100 100 100 Terpolymer of 55 parts of ethylene, 41.9parts of propylene and 3.1 parts of V p ethylidene norbornene. 100 100100 100 Phenolic an t 0. i 0. 5 0. 5 0. 5 Lubricant 1 1 2 5 no. p 0. 5 24 DoLP- 0.5 1 2 A parent vlscosity, poisesxlfi- 6.28 3. 44 3. 19 2. 352. 79 2. 23 1. 61 0. 82 3. 84 2. 37 2. 09 1. 85 eat distortiontemperature C C.) 94 93. 5

1 Copolymer of 40 parts of ethyl acrylate and 60 parts of Z-ethylhexyl 3(Jopolymer 0190 parts of methyl aorylate and parts of butyl acrylateacrylate (mol. wt.=6,760). (mol. wt.=10,230).

2 Homopolymer of lauryl acrylate (mol. wt.=8,930).

. TABLE IV Composition, parts by weight:

Polystyr 50 50 50 i Copolymer of 10 parts of butadiene and 90 parts ofstyrenel. v 50 50 50 Polyethylene 100 100 100 Copolymer of 88 parts oiethylene and 12 parts of vinyl acetate 100 100 100 Lubricant 3 6 D09. 1.5 4 Do. 0. 5 2 Apparent viscosity, poisesXlO- 0.80 0. 72 0.46 17.5 16.814. 9 0 91 0.89 0 77 Heat distortion temperature C.) 84 81 V 35 40 1Apparent viscosity is determined as described earlier with the excep- 3Copolymer 0140 parts of butyl aerylate and 60 parts of lauryl acrylatetion thatthe rheometer is maintained at 160 0. (mol. wt.=6,790).

2 (llopglyrlirlaai 80 parts of butyl acrylate and 20 parts of laurylaerylate I 4 Homopolymer oi octadecyl acrylate (mol. wt.=3,200)

mo.w.=, I .i 7

TABLE V Composition, parts by weight: v

Graft eopolymer of 96 parts of polyvinyl chloride on 4 parts oichlorinated polyethylene Polyacrylic processing aid Epoxidized soybeanoil Q v Barium-cadmium stabilizer. i Phosphate stabilizer Organotinstabilizer a Lubricant 1 a t D0.3 1.5 -5"". a a a 5 1 Apparentviscosity, p01sesX10 6.5 2.0 6.3 1.3 4.75 3.78 2.65 2.86 2. 42 Heatdistort1ontemperatnre'( C.) a 63 65 1 Copolymer of30 parts of ethylacrylate and 70 parts of 2ethylhexyl 5 Homopolymer of lauryl acrylate(mol. wt.=7,400). acrylate (mol. Wt.=4,760). 4 Homopolymer of methylacrylate (mol. wt.=8,920)., 1 Copolymer of 90 parts of methyl acrylateand 10 parts 'oi butyl acrylate (mol. wt.=5,320).

v 'IABLEVI Composition, parts by weight: v1 ,p

. Copolymer of 92 parts of vinyl chloride and 8 parts of vinyl acetate.1 100 i 100 1' 0 a Cellulose acetate butyrate poly 4 I V p p 100 100 100Polystyr 100 100 100 100 Organotin st 2. 5 1 2. 5 2. 5

' 'Lubricant p 3 5 i I 11 A D05... 7 Apparent viscosity, poisesXlO-LHeat distortion temperature C.

1 Apparent viscosity is determined as described earlier with the ex- IHomopolymer of methyl acr late (mol. wt.=9,730). ception that therheometer is maintained at 160 C.- 7 I Homopolymer oi lauryl aery te(mol. Wt.=9,500).

' 2 Copolymer 0t 90 parts oi methyl acrylate and 10 parts of butylacrylate (mol.wt.=2,100). v I

Q I EXaI-nplet Thermoplastic resins A polycarbonate of1,3-di(4-hydr0xyphen- .7 61 J v 1' 7-63,: 64 yl)propane.

Composition, parts by weight: p H 66 A polycarbonate of2,2-di(4-hydroxyphenh 100- .100: 1001100 A ifi fil iiiifi fiffffiifz 165 i a yDp p 1 1 Oopolymer 0140 parts ofbutylacrylate ard 60 partsoilaurylacrylate. 1 8 flu Polyvinyl acetate.

EXAMPLES 65 85 :7 p I Ethyl cellulose. The thermoplastic resins listedbelow in each example 70 p op ate. are mixed on a rolling mill to ahomogeneousblend with Celluloseacetate-butyl'ate- 2 parts by weight,,per 100Iparts by weight of each ther- 72 1 Polypropylene. moplasticresin, of a copolymer of 30 parts of ethyl H 3 PolyheXamfithyleneadlpamldeacrylate and 70 parts 0f 2-ethylhexyl acrylate having a 7 Acopolymer of 4 parts of ethylene and molecular weight of 4690; 75 96parts of vinyl chloridee e 11 TABLEContinued '75 A copolymer of 60 partsof styrene and 40 '40 .parts of. methyl methacrylate. I 76 A copolymerof 30 parts of styrene and 70,

70 parts of acrylonitrile. 77 Polycaprolactarn. a 78 A copolymer of 98parts of methyl methacrylate and 2 parts of methacrylic acid. 79[ Acopolymer of 80 parts of methyl meth-j acrylate and 20 parts.of'glycidyl methacrylate. i

' '80 A'terpolymer of 85 parts of methyl. methacrylate, 11 parts ofacrylonitrile and 4 parts of acrylic acid. 81 A terpolymer of 50 partsof styrene, 35 7 Pa Q q l l 'fl .151 35 9 1 acrylic acid. '82' Aterpolymer of 60 parts of'vinylchlm ride, 20 parts of, acrylonitrile and20 parts of acrylic acid. 83 Poly(a-methylstyrene). 84Poly-4-methylentene-1. I v 85 Polyoctadecene-L1 i" 86 A terpolymer of 25parts of acrylonitrile,

20 parts of butadiene and 55 parts of styrene. I ff; J The resultantthermoplastic-resinous compositions have apparent viscosities which arelower than those of compositions obtained from the thermoplastic resinsin the. absence of the lubricant additive. a

I 2. The composition as defined in claim 1 wherein the 1 liquid.copolymer is. a copolymer. of 1(1). from. about .to

about rs 99nt12 we h Y X .=1iW i??? the alkyl radical contains from 1 toabout12 carbon atoms and (2)" from about 95 to abQutS-percehtby weightof a dissimilar alkyl acrylate wherein the alkyl radical containsfrom-about 3 toabout 24 carbon atoms.

3.' The composition asd'efined in claim lwher'ein the a liquid copolymeris a copolymer of (1) from about '5 to From the foregoing results it isevident that the rela H tive viscosity or melt flow property of thecompositions of this invention is notably superior to thattof theunblended thermoplastic resinous compositions. In addition,

the compositions of the present invention such as :hard- 'about'95'percent by weight of an alkyl acrylate wherein the alkyl radicalcontains from 1 tofabout IZcarBOnatQmS and (2) from about-95 to aboutS-percient by weight of -a dissimilar alkyl acrylate wherein th'ejialkylradical' 'contains from about'3 to about 18 carbon atoms; 7 f l 4. Thecomposition as defined in claim 1 wherein the "copolymer is a copolymerof (1) from about 20 to about 5 0 percent by Weight of an'alkyl acr latewherein the" alkyl radical contains from about-2 to about 8 carbon-atomssimilar ethylenically unsaturated monomer.

7 Tne'cbmpe'sinefi "as defined in claini's' wherein the -vinyl' halidepolymer'ispolyvinyl' chloride, at copolymer-0f Z 92 parts of vinylchloride and 8 partsof vinyl acetatefora it is found that other desiredphysical characteristics of ness, impact strengths and heat distortiontemperatures, are not unduly affected by the incorporation of the lubri-For many purposes, it may be desirable to blend other 4 conventionaladditives with the thermoplastic resinous compositions of the presentinvention. For example, the

properties of the resinous compositions may .be modified byincorporating therewith an'inert filler'such-awglass fibers, groundasbestos, mica and the like, dyes, p1gments,.;

plasticizers, reinforcing materials, stabilizers and the'like. It willbeapparent that compositions containing, suchlj.

' ipolymer 'of methyl methacryla graft copolymer of 96 parts ofpolyvinyl-chloride on 4 parts of chlorinated polyethylene,

8. The composition as defined in cljairnfl l wher n'fsaid resin is apolymer ofrm'ethyl methacr'ylate se1e'ctedfrom the group consisting ofhomopolymers of methylinethacrylate and copolymers of methylmethajcrylatefwith at least one dissimilar ethylenicallyv unsaturated,menomep 1:

9. The'.'composition as defined '11 claim 8 wherein'the as y ims h' l y'homopolymer'. 1 v "10."The composition as defined in clairiiv 1 wherei5 resin is a polymer of an u-monoolefin selected from the groupconsisting of homopolymers of a-monoolefin monoother additives arewithin the scope of this invention. The

compositions may readily be calendered to formsmooth sheets andfabricated into shaped articles by conventional forming techniques, forexample, by blow jection molding, casting and'extrusiom While thisinvention has been described with respect to certain embodiments, it isnot so limited, and it should be understood that variations andmodifications thereof may-"be made Which are obvious to those skilledj-in-th art without departing from the spirit or scopeof "the invention.

= The embodimentsof the'inve'ntion in which anexclu sive property orprivilege is claimed are. defined as follows: L A composition of matterconsisting of aresinwof at least one ethylenically unsaturated monomerand a liquid copolymer of (1) from about 5 to. about 95% byyweight of analkylacrylate wherein the alkyl radical contains'from 1 to a bout 12carbon atoms and (2) from about.- 95 to about 5% by weight of adissimilar alkyl acrylate wherein the alkyl radical contains from about3 to about 24 carbon atoms, where the acrylic copolymer is present inamounts of from about 0.001 to 8.0 parts by weight per 100;;parts byweight of resin; y

molding; in

a l 'r'ners having from -to 24 carbon atoms= and copolymers 9 .5 1 mo omrs with at least one..dissimilanethylenically unsaturated monomer. l 3 vI "Hi The 'eompositiehfas defined in clai'm jl rem the polymer of'the'e-monoolefin is polyethylene-or: acopolyr tr er of 88' parts of ethyleneand rz artspf vinyl acetate.

-12. The composition as defined in claim-1= wherein said resin is 'a"'monovinyl-s'ubstituted aromatic hydrocarbon Po e ek e tronthe roup...consi tingLj ti5b1ym- .erized monovinyl -substituted.aromatichydrocarbon monomers. and ,copolymers of ',such;monornersjwitli at l east one dissimilar ethylenically unsaturatedmonomer. 13. The composition as defined in claim 12 wherein themonovinyl-substituted aromatic hydrocarbon polymer is poly ty en oaconolymer. .ofQ .74parts. of..styrene and.26

parts of a itrile.

" 14;The compositioifas'defined in claim 1 wii'e inj-the liquid}-copolymer is a copolymer "of 30 parts'of" ethyl acrylate and;7 0 partsof 2-ethylhexyl'acryla'te.'-

liquid-copolymer :is a copolymer .of 50 :parts :ofsQ-ethylhexyl acrylateand.50 parts of octadecyl acrylate.

16 The composition as definedin claim lyyh rein the f ta t air il'e hylsi'tionas'defined in claim l wher'e I 18. The composition as defined inclaim 1 wherein the liquid copolymer is a copolymer of 80 parts of butylacrylate and 20 parts of lauryl acrylate.

19. The composition as defined in claim 1 wherein the liquid copolymeris a copolymer of 40 parts of butyl acrylate and 60 parts of laurylacrylate.

20. The composition as defined in claim 1 wherein the resin ispolyvinylchloride.

21. The composition of claim 20 wherein the liquid copolymer has anaverage molecular weight of from about 2000 to about 6000.

22. The composition of claim 20 wherein the liquid copolymer has anaverage molecular weight of from about 3500 to about 5000.

23. The composition of claim 20 wherein the liquid copolymer is acopolymer of ethyl acrylate and 2-ethylhexyl acrylate.

References Cited UNITED STATES PATENTS 2,247,064 6/ 1941 Nowak 2608992,311,249 2/ 1943 Powell 260899 2,439,395 4/ 1948 Leatherman 2608993,050,412 8/ 1962 Coe 260899 3,322,857 5/1967 Coaker et al 2608763,224,996 12/ 1965 Balmer et a1 26031.8 R 3,074,905 1/1963 Douglas 26031.8 R 3,342,853 9/1967 Nemec et al 26031.8 R

FOREIGN PATENTS 237,020 8/1959 Australia 260899 15 HAROLD D. ANDERSON,Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE QRTIFICATE 0F CURRECTION Patent No. 3,809 rDated May 7 1974 Invenwfls) Antonv W. M. Coaker and Elmer E. Cowell Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 5, line 46, "unsaurated" should be corrected to read"unsaturated".

Table V, line 6 under the heading "Composition, parts by weight:" theword "Phosphate" should be corrected to read "Phosphite"; same table,line 12 under the heading "50" the numeral "666" should be corrected toread "66".

b Table VI, line 1 under the heading "53 the numeral "1 0" should becorrected to read "100"; same column, line 8, the numeral "3.55" shouldbe corrected to read "3.35"; same table, last column, the numeral "60"should be entered in the blank.

Column 11, line 2 the numeral "40" at the end of that line should beremoved.

. Column 11, line 3, the numeral "70" at the end of that line should beremoved.

Column 11, line 22 the compound "Poly4methylentenel" should be correctedto read "Poly-4-methylpentene-l".

Column 12 Claim 4 line 2 the word "liquid" should be added before theword "copolymer" first occurrence.

Signed and Scaled this eleventh Day of May 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting ()j'jn'cr ('mnmissiuncruj'lalems and Trademarks

